Electronic structures of single crystalline black phosphorus were studied by state-of-the-art angle-resolved photoemission spectroscopy (ARPES). Through high resolution photon energy dependence measurements, the band dispersions along out-of-plane and in-plane directions are experimentally determined. The electrons were found to be more localized in the $ab$ plane than is predicted in calculations. Beside the $k_z$-dispersive bulk bands, a surface resonant state is also observed in the momentum space. Our results strongly suggest that more details need to be considered to fully understand the electronic properties of black phosphorus theoretically.

• Received 27 May 2014
• Revised 21 July 2014

DOI:https://doi.org/10.1103/PhysRevB.90.085101